Pesticidal compositions

ABSTRACT

PCT No. PCT/EP97/02009 Sec. 371 Date Oct. 13, 1998 Sec. 102(e) Date Oct. 13, 1998 PCT Filed Apr. 21, 1997 PCT Pub. No. WO97/40683 PCT Pub. Date Nov. 6, 1997The present invention relates to novel crop-protecting active ingredient mixtures having synergistically enhanced action, comprising at least two active ingredient components together with a suitable carrier, wherein component I is 1-[[2-(2,4-dichorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (&#34;propiconazole&#34;) and component II is 5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazole (&#34;tricyclazole&#34;); or in each case a salt or metal complex thereof.

This application is a 371 of PCT/E897/02009, filed Apr. 21, 1997.

The present invention relates to novel crop-protecting active ingredientmixtures having synergistically enhanced action, comprising at least twoactive ingredient components together with a suitable carrier, whereincomponent I is

1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole("propiconazole") (ref: Ch. R. Worthing (ed.) The Pesticide Manual, 9thedition, 1991, page 724)

and component II is

5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazole ("tricylazole"); (ref:Ch. R. Worthing (ed.):

The Pesticide Manual, 9th edition, 1991, page 846), or in each case asalt or metal complex thereof.

Surprisingly, it has now been found that the mixtures of components Iand II according to the invention have, in the prevention and control ofplant diseases, not only an additive action but a distinctsynergistically enhanced action.

Advantageous mixing ratios of the two active ingredients are I:II=from30:1 to 1:30, from 1 0:1 to 1:10, preferably I:II=from 3:1 to 1:3 andfrom 1:1 to 1:3.

The present invention relates also to a method of protecting plants fromplant diseases, especially fungal infestation, which comprises treatingthe plants, parts of plants or their surroundings with a component I anda component II, in any desired sequence or simultaneously.

The active ingredient mixtures I+II according to the invention have veryadvantageous properties for protecting plants against diseaseinfestation. The active ingredient mixtures in question can be used toinhibit or destroy the micro-organisms that occur on plants or on partsof plants (the fruit, blossom, leaves, stems, tubers or roots) ofdifferent crops of useful plants, while at the same time parts of plantsthat grow later are also protected against such microorganisms. They canalso be used as dressings in the treatment of plant propagationmaterial, especially seed (fruit, tubers, grains) and plant cuttings(e.g. rice), to provide protection against fungus infections as well asagainst phytopathogenic fungi that occur in the soil. The activeingredient mixtures according to the invention are distinguished by thefact that they are well tolerated by plants and are environmentallyfriendly.

The active ingredient mixtures are effective against phytopathogenicfungi belonging to the following classes: Ascomycetes (e.g. Venturia,Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula);Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Puccinia); Fungiimperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium,Septoria, Cercospora, Altemaria, Pyricularia and Pseudocercosporellaherpotrichoides); and Oomycetes (e.g. Phytophthora, Peronospora, Bremia,Pythium, Plasmopara).

Target crops for the areas of indication disclosed herein comprisewithin the scope of this invention e.g. the following species of plants:cereals (wheat, barley, rye, oats, rice, sorghum and related crops);beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit(apples, pears, plums, peaches, almonds, cherries, strawberries,raspberries and blackberries); leguminous plants (beans, lentils, peas,soybeans); oil plants (rape, mustard, poppy, olives, sunflowers,coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants(marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute);citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables(spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes,potatoes, paprika); lauraceae (avocados, cinnamon, camphor); or plantssuch as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops,bananas and natural rubber plants, as well as ornamentals (flowers,shrubs, broad-leaved trees and evergreens, such as conifers). This listdoes not represent any limitation.

The active ingredient mixtures according to the invention are especiallyadvantageous for the treatment of rice against Pyricularia andRhizoctonia and also Helminthosporium.

The mixtures of compounds of formulae I and II are normally used in theform of compositions. The compounds of formulae I and II can be appliedto the area or plant to be treated either simultaneously or insuccession on the same day, if desired together with further carriers,surfactants or other application-promoting adjuvants customarilyemployed in formulation technology.

Suitable carriers and adjuvants can be solid or liquid and are thesubstances ordinarily employed in formulation technology, e.g. naturalor regenerated mineral substances, solvents, dispersants, wettingagents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying an active ingredient mixture comprisingat least one of each of the active ingredients I and II is applicationto the parts of the plants that are above the soil, especially to theleaves (foliar application). The frequency and rate of applicationdepend upon the biological and climatic living conditions of thepathogen. The active ingredients can, however, also penetrate the plantthrough the roots via the soil or via the water (systemic action) if thelocus of the plant is impregnated with a liquid formulation (e.g. inrice culture) or if the substances are introduced in solid form into thesoil, e.g. in the form of granules (soil application). In order to treatseed, the compounds of formulae I and II can also be applied to theseeds (coating), either by impregnating the tubers or grains with aliquid formulation of each of the active ingredients in succession, orby coating them with an already combined wet or dry formulation. Inaddition, in special cases, other methods of application to plants arepossible, for example treatment directed at the buds or the fruittrusses.

The compounds of the combination are used in unmodified form or,preferably, together with the adjuvants conventionally employed informulation technology, and are therefore formulated in known mannere.g. into emulsifiable concentrates, coatable pastes, directly sprayableor dilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granules, or by encapsulation in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering, coatingor pouring, are chosen in accordance with the intended objectives andthe prevailing circumstances. Advantageous rates of application of theactive ingredient mixture are generally from 50 g to 2 kg a.i./ha,especially from 100 g to 1000 g a.i./ha, more especially from 250 g to700 g a.i./ha. In the case of the treatment of seed, the rates ofapplication are from 0.5 g to 1000 g, preferably from 5 g to 100 g, a.i.per 100 kg of seed.

The formulations are prepared in known manner, e.g. by homogeneouslymixing and/or grinding the active ingredients with extenders, e.g.solvents, solid carriers and, where appropriate, surface-activecompounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates, such as dibutyl phthalate or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins,alcohols and glycols and their ethers and esters, such as ethanol,ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones,such as cyclohexanone, strongly polar solvents, such asN-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as wellas vegetable oils or epoxidised vegetable oils, such as epoxidisedcoconut oil or soybean oil; or water.

The solid carriers used, e.g. for dusts and dispersible powders, arenormally natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite, and suitable nonsorbent carriers are, for example, calciteor sand. In addition, a great number of pregranulated materials ofinorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending upon the nature of the compounds of formulae I and II to beformulated, suitable surface-active compounds are non-ionic, cationicand/or anionic surfactants having good emulsifying, dispersing andwetting properties. The term "surfactants" will also be understood ascomprising mixtures of surfactants.

Particularly advantageous application-promoting adjuvants are alsonatural or synthetic phospholipids of the cephalin and lecithin series,e.g. phosphatidylethanolamine, phosphatidylserine, phosphatidylglyceroland lysolecithin.

The agrochemical compositions normally comprise 0.1 to 99%, especially0.1 to 95%, compounds of formulae I and II, 99.9 to 1%, especially 99.9to 5%, of a solid or liquid adjuvant and 0 to 25%, especially 0.1 to25%, of a surfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The Examples which follow serve to illustrate the invention, "activeingredient" denoting a mixture of compound I and compound II in aspecific mixing ratio.

Formulation Examples

    ______________________________________                                        Wettable powders      a)      b)     c)                                       ______________________________________                                        active ingredient     25%     50%    75%                                      [I:II = 1:3 (a), 1:2 (b), 1:1 (c)]                                            sodium lignosulfonate  5%      5%    --                                       sodium lauryl sulfate  3%     --      5%                                      sodium diisobutylnaphthalenesulfonate                                                               --       6%    10%                                      phenol polyethylene glycol ether                                                                    --       2%    --                                       (7-8 mol of ethylene oxide)                                                   highly dispersed silicic acid                                                                        5%     10%    10%                                      kaolin                62%     27%    --                                       ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        Emulsifiable concentrate                                                      ______________________________________                                        active ingredient (I:II = 1:6)                                                                      10%                                                     octylphenol polyethylene glycol ether                                                                3%                                                     (4-5 mol of ethylene oxide)                                                   calcium dodecylbenzenesulfonate                                                                      3%                                                     castor oil polyglycol ether                                                                          4%                                                     (35 mol of ethylene oxide)                                                    cyclohexanone         30%                                                     xylene mixture        50%                                                     ______________________________________                                    

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

    ______________________________________                                        Dusts             a)        b)     c)                                         ______________________________________                                        active ingredient  5%        6%     4%                                        [I:II = 1:6 (a), 1:2 (b), 1:10 (c)]                                           talcum            95%       --     --                                         kaolin            --        94%    --                                         mineral filler    --        --     96%                                        ______________________________________                                    

Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

    ______________________________________                                        Extruder granules                                                             ______________________________________                                        active ingredient (I:II = 2:1)                                                                   15%                                                        sodium lignosulfonate                                                                             2%                                                        carboxymethylcellulose                                                                            1%                                                        kaolin             82%                                                        ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

    ______________________________________                                        Coated granules                                                               ______________________________________                                        active ingredient (I:II = 1:10)                                                                    8%                                                       polyethylene glycol (mol. wt. 200)                                                                 3%                                                       kaolin               89%                                                      ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

    ______________________________________                                        Suspension concentrate                                                        ______________________________________                                        active ingredient (I:II = 1:8)                                                                      40%                                                     propylene glycol      10%                                                     nonylphenol polyethytene glycol ether                                                                6%                                                     (15 mol of ethylene oxide)                                                    sodium lignosulfonate 10%                                                     carboxymethylcellulose                                                                               1%                                                     silicone oil (in the form of a 75%                                                                   1%                                                     emulsion in water)                                                            water                 32%                                                     ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Biological Examples

A synergistic effect exists whenever the action of an active ingredientcombination is greater than the sum of the actions of the individualcomponents.

The action to be expected E for a given active ingredient combinationobeys the so-called COLBY formula and can be calculated as follows(COLBY, S.R. "Calculating synergistic and antagonistic responses ofherbicide combination". Weeds, Vol. 15, pages 20-22; 1967):ppm=milligrams of active ingredient (=a.i.) per litre of spray mixtureX=% action by active ingredient I using p ppm of active ingredient Y=%action by active ingredient II using q ppm of active ingredient.

According to Colby, the expected (additive) action of active ingredientsI+II using p+q ppm of active ingredient is ##EQU1##

If the action actually observed (O) is greater than the expected action(E), then the action of the combination is superadditive, i.e. there isa synergistic effect.

EXAMPLE B-1 Action Against Puccinia recondita on Wheat

a) Residual-protective Action

6 days after sowing, wheat plants are sprayed to drip point with anaqueous spray mixture prepared from a wettable powder formulation of theactive ingredient mixture and infected 24 hours later with a uredosporesuspension of the fungus. After an incubation period of 48 hours(conditions: 95-100% relative humidity at 20°) the plants are placed ina greenhouse at 22°. Fungus infestation is evaluated 12 days afterinfection.

b) Systemic Action

5 days after sowing, wheat plants are watered with an aqueous spraymixture prepared from a wettable powder formulation of the activeingredient mixture. Care is taken that the spray mixture does not comeinto contact with parts of the plant that are above the soil. The plantsare infected 48 hours later with a uredospore suspension of the fungus.After an incubation period of 48 hours (conditions 95-100% relativehumidity at 20°) the plants are placed in a greenhouse at 22°. Fungusinfestation is evaluated 12 days after infection. The active ingredientmixtures according to the invention exhibit a good synergistic action.

EXAMPLE B-2 Action Against Rhizoctonia solani on Rice Plants

Approximately two-week-old rice plants are placed together with the soilaround the roots in a vessel filled with a spray mixture of the activeingredient mixture. After 96 hours, the rice plants are infected with aconidia suspension of the fungus. Fungus infestation is evaluated afterincubating the infected plants for 5 days at 95-100% relative humidityand about 24° C. The active ingredient mixtures according to theinvention exhibit a distinctly enhanced action.

EXAMPLE B-3 Residual-protective Action Against Venturia inaequalis onApples

Apple cuttings with 10-20 cm long fresh shoots are sprayed to drip pointwith an aqueous spray mixture prepared from a wettable powderformulation of the active ingredient mixture and infected 24 hours laterwith a conidia suspension of the fungus. The plants are incubated for 5days at 90-100% relative humidity and stood in a greenhouse for afurther 10 days at 20-24°. Fungus infestation is evaluated 12 days afterinfection. The active ingredient mixtures according to the inventionexhibit a distinctly enhanced action.

EXAMPLE B-4 Action Against Pyricularia oryzae on Rice Plants

Approximately two-week-old rice plants are placed together with the soilaround the roots in a vessel filled with a spray mixture of the activeingredient mixture. After 96 hours, the rice plants are infected with aconidia suspension of the fungus. Fungus infestation is evaluated afterincubating the infected plants for 5 days at 95-100% relative humidityand about 24° C. The results are shown in the following Table.

    ______________________________________                                                                   %      %      SF                                   propiconazole                                                                          tricyclazole                                                                            ratio in                                                                              activity                                                                             activity                                                                             (Colby)                              (mg a.i./l)                                                                            (mg a.i./l)                                                                             mixture observed                                                                             expected                                                                             O/E                                  ______________________________________                                        0.6                         0                                                 2                           2                                                 6                          15                                                 20                         22                                                 60                         25                                                          0.2                3                                                          0.6               13                                                          2                 59                                                          6                 82                                                 0.6      0.2       3:1     56      3     18.7                                          0.6       1:1     60     13     4.6                                           2         1:3     72     59     1.2                                           6          1:10   88     82     1.1                                  2        0.2       10:1    36      5     7.2                                           0.6       3:1     47     15     3.1                                  6        0.2       30:1    36     18     2.0                                           0.6       10:1    51     26     2.0                                  20       0.6       30:1    56     32     1.8                                  ______________________________________                                    

What is claimed is:
 1. A composition comprising a synergisticallyeffective microbicidal amount of a mixture comprising at least twoactive ingredient components together with a suitable carrier, whereincomponent Iis1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazoleand component II is 5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazoleorin each case a salt or metal complex thereof; wherein the ratio byweight of I:II is from 30:1 to 1:10.
 2. A composition according to claim1, wherein the ratio by weight of I:II is from 10:1 to 1:10.
 3. Acomposition according to claim 2, wherein the ratio by weight of I:II isfrom 3:1 to 1:3.
 4. The composition according to claim 1 furthercomorising an adjuvant.
 5. The composition according to claim 4 whereinthe adjuvant comprises a phospholipid.
 6. A method of protecting plantsfrom plant diseases, which comprises treating the plants, parts ofplants, seeds plant cuttings or their surroundings with asynergistically effective microbicidal amount of a mixture of componentI and component II according to claim 1, in any desired sequence orsimultaneously.
 7. The method according to claim 6 of treating rice toprotect the rice against phytopathic fungi selected from the groupconsisting of Pyricularia, Rhizoctonia, Helminthosporium, and mixturestherof.
 8. The method according to claim 6 wherein the treatmentcomprises a foliar application or a soil application of the mixture ofcomponent I and component II.